Process of beneficiating douglas fir wax and product thereof



Dec. 21, 1954 KURTH 2,697,717

PROCESS OF BENEFICIATING DOUGLAS FIR WAX AND PRODUCT THEREOF Filed July 2, 1951 CRUDE DOUGLAS-FIR WAX I II III I I MELT DISSOLVE IN A SUSPEND IN AQUEOUS SOLVENT FOR WAX MEDIUM AS BY MELTING IN HOT WATER OR EMULSIFYING REACT IN THE PRESENCE OF MOISTURE WITH A MINERAL OR ORGANIC ACID HAVING A pH OF LESS THAN ABOUT 5, 6.9. SULFURIC ACID, SULFUROUS ACID, OR OXALIC ACID I DECOLORIZED WAX 1 DECOLORIZED WAX DECOLORIZED WAX ADD AT LEAST ABOUT O.I% BY WEIGHT OF A BASIC ACTING COMPOUND OF LEAD OR A GROUP II METAL, 8.9. CALCIUM OXIDE, MAGNESIUM OXIDE OR ZINC OXIDE HEAT AND HEAT AND HEAT AND AGITATE AGITATE AGITATE SEPARATE MOLTEN SEPARATE EXCESS SOLID COOL AND SEPARATE WAX FROM EXCESS SOLID BASIC ACTING COMPOUND SOLID wAx FROM BASIC ACTING COMPOUND FROM SOLVENT, AND AQUEOUS MEDIUM REMOVE SOLVENT BENEFICIATED DOUGLAS FIR WAX WHICH IS HARD, HIGH MEL'I'ING OR LIGHT IN COLOR INVENTOR.

ERVIN F. KURTH Attorney United States Patent '0 PROCESS OF BENEFICIATING DOUGLAS WAX AND 'PRGDUCT THEREOF Ervin F. Kurtll, (Ion-vallis, -Oreg., assignor to State ofzOregon, acting by and through the Gregor! State Board of Forestry Application July 2, 1951, Serial No. 234,805

33 Claims. (Cl. 260-424) The present invention relates to a process of beneficiating Douglas fir wax, and to the beneficiated wax products resulting therefrom, i. e., wax products which have improved melting point, hardness, color and other properties.

The Douglas fir wax which is the subject matter of the present invention is a vegetable wax derived from the bark and wood of the tree. 'It is fully disclosed in my co-pending U. S. Patent application Serial No. 152,482, filed March 28, 1950,, for Extraction of Valuable Products From Bark. As is set forth in the aforesaid patent application, a valuable wax product may be obtained from thebark and wood of the Douglas 'fir by extracting it with suitable selective solvents for the wax. By :this procedure there may be obtained a wax product in a yield of upto about 9% by weight based on the dry weight of the bark.

This wax product may be separated into two component wax fractions, 'i. e. a first wax fraction which is soluble in the lower aliphatic hydrocarbon solvents, the aromatic hydrocarbon solvents, and the halogenated aliphatic hydrocarbon solvents, and a second wax fraction which is insoluble in the lower aliphatic hydrocarbon solvents but soluble in the aromatic hydrocarbon solvents and the halogenated aliphatic hydrocarbon solvents. The first wax product may be obtained in ,a yield of .up to about 6% by weight and the second wax product in a yield of up to about 3 by weight based onthe dry weight of the bark. The first wax product appears to .be composed principally of lignoceryl alcohol, lignoceric acid, lignoceryl lignocerate, ferulic acid,.and lignocerylferulate. It is yellow to tan in color and is similar in appearance and melting point to beeswax. Furthermore, itis the full equivalent of the latter for many uses including themanufacture of floor waxes, candles, wax emulsions, polishes, coating and moisture proofing agents, cosmetic creams, and the like.

The second wax product, i. e. that which is insoluble in the lower aliphatic hydrocarbon solvents, has a more complex chemical composition than does the first wax product, being composed insofar as is known of phenolicfatty acidandhydroxy fatty acid complexes. fit is brown in color and is useful 'in general for applications in which a colored wax is suitable, for example, in the formulation of moisture sealing compositions.

In my U. S. Patent No. 2,526,607 for Waxes and Their Production from Wood Waste, 21 modified Douglas fir wax is described which is produced as a by-product of a wood treating process wherein the wood is converted first to sugars and ultimately to alcohol. In accordance with this process, the whole wood, including some bark, is chipped and then hydrolyzedwith a dilute mineral acid for the selective conversion of itscellulosic and 'hemi-cellulosic content to sugars, leaving a 'lignin residue. The sugar product may be used directly vas molasses for feeding stock and the like, or alternatively 'it may be fermented to ethyl alcohol.

The lignin residue obtained in the-foregoing-mannerhas, however, a substantial content of wax which may be-separated by extraction with selective wax solvents. There thus may -be obtained a whole wax product, or two wax fractions, the firstbeing soluble in the lower aliphatic hydrocarbon solvents, the aromatic hydrocarbon solvents and the halogenated aliphatic hydrocarbon solvents,.and the second being insoluble in the lower .aliphatic :hydrocarbon solvents but soluble in the aromatic hydrocarbon solvents. In composition these fractions are somewhat analogousxto those obtained by the direct solvent extraction of the bark and wood as described above. The first wax fraction, however, contains a lesser proportion of lignoceryl lignocerate and lignoceryl ferulate, and the phenolic-fatty acid complexes of the second wax fraction have been modified in an unknown manner by the acid hydrglysis (to which the wood and bark have been subjecte All of the foregoing waxes and wax fractions are suitable for use in the presently described beneficiation process, however, and are included .by definition in the term Douglas fir wax used herein.

The foregoing waxes and wax fractions are potentially available at very low cost, in quantities of millions of pounds annually, as-va lua-ble by-products of lumbering operations. However, it is desirable for some purposes that the properties of the wax, particularly the hardness, melting point, color, and ability to form gels be improved. Thus, a better floor polish may be obtained if the wax first is hardnened and itsmelting point raised. Similarly, in many coating and polishing operations, it is desirable that the color of the wax be lighter than it is as originally obtained from the extraction procedures. This improvement or beneficiation must be obtained, furthermore, Without afiecting' adversely the other properties of the wax such as its solvent retention, its stability to atmospheric agents and chemical substances, its texture, and its freedom from greasiness and tackiness.

It therefore -is a principal object of the present invention to provide a beneficiated Douglas fir wax having a relatively high melting point, improved hardness, improved color, or improved gel forming properties.

It is another object of this invention to provide a process for beneficiating Douglas ,fir wax which process is easlly elfectuated in readily available equipment at minimum cost.

Still another object of the present invention is the provision of a process for beneficiating Douglas fir wax which may be controlled to produce a desired degree of improvement of a selected property such as hardness or melting point, this result being obtainable without the necessity of compounding the wax with waxes of other types.

It 'is another object of the present invention to provide a process 'for improving the hardness or melting point of Douglas fir wax without adversely afiecting the other properties of the wax.

It is another objectof this invention to provide a process for *beneficiating Douglas fir wax to produce an inexpensive wax product which in many instances may be used 111 place of conventional waxes, such as beeswax, carnauba wax, candelilla wax and the like in their diverse applications.

'The manner 'in which the foregoing and other objects of this invention are accomplished will be apparent from the following specification and claims considered together with the accompanying drawing comprising a flow plan of the presently described process.

,As is apparent from .the flow plan, a selected one of at least three different procedures may be employed in executing the presently described process of beneficiatng Douglas .fir wax, depending upon whether the wax is treatedin molten form, dissolved in a suitable solvent, or mixed with water either in emulsion form or as ,molten wax. in any of .these procedures, when it is desired to dQFOlOItIZG IhQ wax, it 'is reacted with a suitable ,mineral acid or organic acid, e. .g. sulfurous acid or oxalic acid. This forms .a ,product which is lighter in color than the original material and satisfactory for many commercial uses with respect to this importantproperty.

The wax with or without a preliminary decolorizing treatment-is treated with at least about 0. 1%, preferably from about 0.1% .to about 10.0% by weight of a basic acting compound of lead or of a metal found in .group II {of the periodic table, e. g. calcium oxide, magnesium oxide or .zinc :oxide. The treatment .is carried out at a temperature at which :the metallic compound is reactive with the wax. This may be ;a temperature of .at least about the melting point of the wax, but below its ,decomposition temperature. During the treatment the wax is stirred or otherwise .agitated withthe :metallic compound to secure intimate ;contact1of the reacting materials.

After the recation is complete, the wax is separated from any excess metallic compound which may be present, and from the reaction medium, where such has been employed. If molten wax has been treated with a solid metallic compound, it may be separated therefrom by decanting, filtering, centrifuging, or other suitable method after which it may be cooled and solidified. 1f the wax has been dissolved in a suitable solvent and then treated with the metallic compound, the excess of the latter may be removed by filtering or other suitable procedure. Thereafter the solvent may be separated from the wax by fractional distillation, steam distillation or the like.

If, however, the wax has been reacted with a metallic compound in an aqueous medium, as by treating an emulsion of the wax or a suspension of the melted wax in water, the wax may be separated directly from the aqueous medium. This may be accomplished in a liquid separator or by cooling the mixture and removing the solid wax.

Whichever of the foregoing procedures has been employed, the final product is a wax which is light in color and which, as compared with the starting material, and vegetable waxes in general, is relatively hard or high melting. Thus, whereas the original melting point of the wax may have been about 57 C., the final melting point after the herein described treatment has been applied may be as much as 100 C., an increase of over 40 C. Furthermore, whereas the original hardness may have been such as to give a standard penetrometer reading at 25 C. of about 1.0 millimeter, the final hardness may be such as to obtain a reading made under the same conditions of as little as 0.1 millimeter. These advantages are gained, furthermore, without adversely affecting the other properties of the wax.

Considering now the foregoing procedure in further detail and with particular reference to the flow plan:

PROCEDURE I In accordance with procedure I of the fiow plan the wax is beneficiated in the molten state. If it is the hexane soluble fraction of Douglas fir wax, it may first be bleached by a preliminary treatment with an acid material. The acid employed may comprise a mineral or organic acid or acid salt having a pH of less than about 5 which is non-degrading to the wax. Preferably, the acid should be substantially insoluble in the wax since if it is soluble therein it tends to remain as an impurity, lowering the melting point of the wax unless precautions are taken to remove it completely.

Illustrative of suitable mineral acids for the purpose of the present invention are sulfuric acid, sulfurous acid, hydrochloric acid, phosphoric acid, phosphorous acid, dilute nitric acid, and the like. Illustrative of suitable organic acids for the purpose are oxalic acid, acetic acid, chloracetic acid, propionic acid, formic acid and the like. Preferred members of these groups comprise sulfuric acid, sulfurous acid, or oxalic acid. These and other mineral and organic acids may be used singly or in combination with each other.

In applying the acidic decolorizing agent, the wax which originally has a melting point of between about 55 C. and about 60 C. may be placed in a suitable receptacle and melted. An aqueous solution of the particular acid material used then is mixed with the molten wax and the resulting mixture stirred at a temperature of between about the melting point of the wax and the boiling point of the acid until the pH of the entire mixture has been reduced to a level of below about 5. The time required to obtain this result may be determined by visual observation, the reaction being completed when no further decolorization takes place.

Alternatively, the acid decolorizing treatment may be carried out using the gaseous anhydride of the acid where such is available. Thus sulfur dioxide may be bubbled through a quantity of the molten wax which as usually prepared has an inherent moisture content of from l-5% by weight. The temperture in this case may be between the melting point of the wax and the boiling point of water. The reaction time is that required to complete the bleaching operation as determined by visual observation which in the usual case is about minutes.

After the bleaching step has been carried out, the residual aqueous acid solution, if such has been employed, may be separated from the wax, preferably after cooling the mixture so that the wax is in solid form. If the acid is substantially insoluble in the wax, one or two washings v C. However, during of the decolorized wax with water are sutficient to remove any excess acid. If, however, the acid is substantially soluble in the wax, as in the case of some of the aliphatic organic acids, repeated washing with hot water may be desirable to remove all traces of the acid. The removal of this material is desirable since it may interfere with the action of the basic acting compound employed in the next treating step. Where the wax has been bleached by the foregoing acid treatment, its color is lightened from an original brown to a light cream color, which improves its as polishes and the like.

After bleaching (or without it if a light colored wax is not particularly needed) the wax is treated with a basic acting compound for the purpose of increasing its melting point or hardness or both. Suitable materials for this purpose comprise in general the basic acting compounds of lead and of the group II metals of the periodic table, such metals including beryllium, magnesium, calcium, strontium, barium, zinc, cadmium and mercury. The term basic acting compounds of these metals obviously comprehends the oxides, hydroxides, and carbonates thereof. It also comprehends their peroxides where such exist. Preferred basic acting compounds of the above group comprise the oxides and hydroxides of calcium, magnesium and zinc.

In applying the basic acting compounds to the process of the present invention, they preferably are first pulverized to a particle size of less than about -40 mesh, since otherwise the wax tends to form a coating about the particles, inhibiting their action. Where procedure I is followed, the pulverized basic acting compound is added to the melted wax in amounts of at least about 0.1 preferably between about 0.5% and about 3.0% by weight of the wax. At least about 0.5% is necessary in most instances to secure a substantial increase in melting point or hardness. During the hardening operation the effective fraction of the basic acting compound dissolves in the wax. Therefore if more than about 3.0% is employed the surplus remains in the wax as a solid residue. For some uses this desirably should be removed and it therefore is preferred not to use too large an excess.

During the reaction, the mixture of melted wax and metallic basic acting compound is stirred or otherwise agitated while heating to a temperature sufficient to keep the wax molten, but insuificient to decompose it. Thus, the initial heating temperature may be slightly above the original melting point of the wax, i. e. above about 60 the reaction the mixture tends to freeze as the melting point of the wax increases and it therefore is necessary to increase the reaction temperature. A preferred range for this purpose is between about 75 C, and about 150 C.

The reaction is continued until it is complete, which requires in the usual case at least about 2 minutes. If any unreacted basic acting compound remains after the reaction period has elapsed, the mixture is permitted to stand whereupon the basic acting compound settles to the bottom of the reaction vessel and the molten wax may be removed by decantation. Alternatively, the molten mixture may be filtered or otherwise treated for the removal of the solid basic material. The clear wax then is cooled, whereupon a beneficiated product of relatively high melting point, or hardness, or both is obtained.

PROCEDURE II In Procedure II of the flow plan the wax is beneficiated while dissolved in a suitable solvent.

Thus the wax is dissolved in a suitable neutral solvent which, as indicated above, may be a lower aliphatic hydrocarbon solvent, such as petroleum naphtha or a normally liquid aromatic hydrocarbon solvent, such as benzene or toluene. A sufiicient amount of solvent is employed to dissolve the wax and form a solution having a favorable viscosity for the subsequent treatment.

A suitable solution, for example, may comprise one in which 10 parts by weight of wax is dissolved in about 100 parts by weight of solvent. If it is desired to obtain a wax product which is solid, the solvent preferably should be low boiling, as for example hexane or a petroleum naphtha fraction boiling at between about 60 and about C. It will be apparent that such a solvent may be removed readily by distillation or heating after the reaction is complete If, however, it is deslred to obtain a wax paste as a suitability for many applications such,

product,.a. higher boiling: solvent may. be :used... Suclra. commercially under I the.

in the Wax to form a paste which doesnot crack or dry out upon standing and therefore is suitable for use in polish compositions andthe like.

If the wax solution is to be subjected toa preliminary decolorization treatment, it is treatedwith an acid decolorizing agent such as sulfurous acid, sulfuric acid; or oxalic acid as above. described. This is accomplished by agitating the wax solution with a dilute aqueous solution of acid material in amount-sufficient to reduce the pH of the mixture to a value of less than about 5. The bleaching reaction preferably is carried out abatemperature above room' temperature and up to' about the boiling point ofthe lower boiling constituents of the mixture. After the reaction is complete, as evidenced" by failure of the mixture-to become further' decolorized, the acidsolution is separated from the wax solution'an'd,

if necessary or desirable, the latter may be washed with water to free it from residual quantities of acid.

The decolorized wax then may be hardened by treatment with a basic acting compound of'theclassdescribed above in connection with Procedural of-thefi'ow plan, i. e. a basic acting compound of lead or of a group'II metal, preferably an oxide or hydroxide of calcium, magnesiunror zinc. solvent is heated to a temperature of between about room temperature and the boilingppoint of the solvent and maintained at that temperature while it is contacted with the basic acting'compound. Suitable contact may .be obtained by passing the hot waxsolution over or through abedofthe basic acting compound; by

introducing the basic acting compound in powder form into the hot solution and stirring or otherwise agitating to insure contact betweenthe reactants; or bymixing together the hot solution-of waxand solvent with an aqueous solution or suspension of the finely divided basic. acting compound.

As before, at least about 0.1% of basic acting compound'is' employed, based upon the weight of the wax. In the usual' case, from about 0.5%' to about 3.0% of this willreact with the wax,.the excess remaining as a solidresidue. I

Next the wax solution which has been treated with the basic acting compound is separated from the latter by.

anysuitable' method. If it has been passed through a bed of" the materials the effluent wax solution will be substantially free of suspended solids and ready for furthcr processing. If the hot solution has been agitated with a quantity'of the powderedbasicac-ting compound, it is permitted to settle-after which the wax solution may be separated from the solid residue by. decantation, filtration or otherwise;

If the reaction between the two'materials has been effectedby'a'gitating thewax solution with an aqueous solution or suspension of a basic acting compound, the mixtureis'permitted to settle. Thereupon it forms two layers: an upper layercomprising the wax solution together with any excess'basic acting compound and a lower aqueous layer. The wax-containing layer may be separated from the aqueous layer, whereupon it is ready for further processing.

The wax'rnay be separated from any residual solids by filtration, and thereafter from the solvent in which it is'contained by fractional distillation, the solvent being recycled to the treatment of a further quantity of .wax. Alternatively, the solvent'may be removed by steam distillation in which case there is formed a distillate fraction comprising molten Waxadmixed with a small amount of water. The" distillate layer is separated and the S01 vent recycled. The water and any solid material are separated from the wax fraction, which then is cooled until it solidifies.

It will be apparent. that the above described: procedure, i. e. Procedure II of the flow plan, is a preferred procedure because it'may be eifectuated. rapidly and'continuously. Thus the wax may be dissolved in' a solvent, e. g. hexane or Stoddard Solvent and bleached by agitating theresulting'solution with' anacid material as above described. Thebleached. wax; solution. then..is

washed. with;.water and passed through. .or .1 over. a: bed:

To this end thesolution of wax in containing the basic: acting :compound maintainedat aselected. temperature: level; The action occurringi in the bed is substantially instantaneoussotthat the. eifluent wax material maybe withdrawn and distilled for removal of part-or all of the volatile solvent: The latter then may be recycledto the treatment of afurther. quantity of wax while the beneficiated wax may berecovered. and converted by cooling-to a solid product or paste.

PROCEDURE III Inaccordance with Procedure I II'of the .fiow-plan the wax is subjected tothe various beneficiating treatments. described hereinafter firstbeingplaced in an aqueous. medium. Thus it is emulsifiedwith water at'ordinary temperatures, or, preferably, it maybe mixed' withhot water, whereupon it melts. In either case the aqueous. suspension or mixture of wax is reacted'with a mineral acid or organic acid havingapH of lessthan about. 5, e. g. sulfurous acid or oxalic acid, at a temperature of. up to about the boiling temperature of the. aqueousmixture. The reaction mixture is stirred until the reaction. is complete. This accomplishes the bleaching off'th'e. Wax and at'the same time may liberate phenolic hydroxyl' groups and carboxyl groups for reactionwith'the basic acting compound in the subsequent hardening step.

The wax'is separated from the acid bleaching agent in any suitable manner, as by cooling the. mixture whereupon thewax solidifies and may readily: be rem'ovedfrom the aqueous acidmedium. Alternatively; it may be maintained molten whereupon it-forms a separate layer above the aqueous acid solution; The latter then may be withdrawn, leaving-the molten wax:

The'rnolten'is washed with water until any residual acid treating agent'hasbeen removed. It then is emulsified or melted With a further quantity of waterandagitatedwith a basic acting compound of lead ora group,- II-'metal,.e. g. an oxide orhydroxide of calcium, mag-,-- nesium or zinc.

As in the case of Procedures I and II the treatment is effectuated using at least about 0.1% preferably from about 0.5% to about 3.0% of .the basic actingcompound. The reaction temperature may be betweenaboutratmosr:

pheric.temperature and the boilingpoint of.the.rnixture;.

preferably at a temperature approaching the. boiling point since at that temperature the reaction-takes place much more rapidly.

After the reaction'is complete, i.. e..after. a: reaction period of at least about 2 minutes,..the wax iszseparated'. from the aqueous layer either. after. cooling to. solidifyit, or while-it remains in the moltenstate. A'nyexcess: solid basic acting compound will be present in thewax. layer and therefore is removed from the latter. The wax then maybe freed from'the excess basic acting compound and by vacuurn'evaporation from anyresidual moisture. This leaves the beneficiatedwax asthe desired I product.

The processof the presentinvention and theproducts; thereof are illustrated in the following exampleswhereina, parts are given in parts by weight and the hardness of the wax is determined as millimeters of needle penetration in a penetrometer as described in.A. S. T. N. methodof-test D525 gram weightfor 5. secondsat 25 C.).

Example 1.-Sulfur0us acid calcium oxide 10 parts of a Douglas .fir: wax fraction:which.is:soluble in. the lower aliphatic hydrocarbon solvents Was-dissolved in 100 parts petroleum naphtha boiling at.60100. C. To. the resulting solution was added 50 parts of a 1% by weight aqueous solution of sulfurous acid. The two solutions .were. mixed at room. temperature and maintained atithattemperature with agitation for about 5 minutes. The naphtha solution thenwas separated from the aqueous sulfurous acid. solution. and washed with watertoremove any excess sulfurous acid.

Next the naphthasolution of wax was subjected to a hardening treatment wherein it was mixed withlparts of solid calcium oxide in the form of a -320 mesh pow-- der. The mixture was heated to a temperature of'about 60 C. .and'stirred for a time period of 10 minutes; Thereafter: it was permitted to settle, whereupon the solid calcium oxide separatedat 'the bottom so' that'the super natanttnaphthasolution could be decanted. 1

Finally, the: naphtha solvent was separated from the solution by fractional distillation leaving a residue of wax':

Whereas the-original .wax :wasbrown in color, had a. melt ing point of 5657 C. and a hardness of 1.0 mm., the final product was cream colored, melted at 82-85 C. and had a hardness of 0.6 mm.

Example 2.-Oxalic acid, calcium oxide 10 parts of hexane soluble Douglas fir wax was melted and boiled for 10 minutes with 100 parts of a 0.5% by weight aqueous solution of oxalic acid. The bleached mixture was cooled below the melting point of the wax. Thereafter the acid solution was separated and the residual solid wax remelted and washed with hot water to remove any excess acid. The wax then was cooled until it solidified and separated from the wash water, whereupon it was ready for the hardening treatment.

The bleached wax then was hardened by treatment with calcium oxide. To this end it was melted and maintained at a temperature of 90 C. while being agitated with 2 parts of 320 mesh calcium oxide powder. The reaction time was 10 minutes. After settling, the molten wax was decanted from any excess solid calcium oxide. It then was cooled, giving a solid cream-colored wax product having a melting point of 82-83" C. and a hardness of 0.6 mm. The original wax was dark brown in color, had a melting point of 5657 C. and a hardness of 1.2 mm.

Example 3.Calcium oxide, wax solution A quantity of the hexane soluble wax was treated directly with a hardening agent without a preliminary decolorizing treatment. 10 parts of the wax were dissolved in 100 parts of hexane and treated for 10 minutes at a temperature of 50 C. with 1.5 parts of powdered calcium oxide. At the end of this time the wax solution was separated from any calcium oxide residue and the solvent removed by fractional distillation. The resulting wax product had a melting point of 82-83 C. and a hardness of 0.7 mm., as compared to an original melting point of 56-57 C. and an original hardness of 1.2 mm.

Example 4.-Calcium hydroxide The procedure of Example 3 was repeated, using however, calcium hydroxide in place of calcium oxide. In this case the product had a melting point of 8283 C. and a hardness of 0.7 mm.

Example 5 .-M agnesium oxide The procedure of Example 3 was repeated, using however, 1.0 part of magnesium oxide in place of the calcium oxide of that example. The result was a hardened wax mglting at 7475 C. and having a needle penetration of 0. mm.

Example 6.Magnesium hydroxide The procedure of Example 3 again was followed using in place of the calcium oxide of that example 1.5 parts of magnesium hydroxide. This resulted in the formation of a product having a melting point of 7475 C. and a hardness of 0.5 mm.

Example 7.Magnesium carbonate 100 parts hexan soluble Douglas fire wax was melted in 100 parts hot water and 2 parts magnesium carbonate as an aqueous suspension added with stirring. The solution was boiled for minutes and cooled. The water was separated from the wax by decantation. The solid wax product was cream colored and melted at 74-75" C. Its hardness was 0.6 mm.

Example 8.--Magnesium oxide, molten wax 100 parts of wax were melted together with 2 parts by weight of magnesium oxide powder. The molten mixture was maintained with agitation at a temperature of 95 C. for a time of minutes, after which it was decanted to remove the excess magnesium oxide. After cooling the melting point of the solid product was 74-75 C. and its hardness 0.5 mm.

Example 9.Magnesium oxide, aqueous wax suspension 250 parts hexane soluble Douglas fir wax was melted in a steam bath and poured into two liters of a water suspension containing 3.75 grams of magnesium oxide (1.5% by weight). The mixture Was boiled for 10 minutes after which it was cooled and the aqueous layer decanted.

The product was dried with the water pump and a steam bath. Its melting point was 7475 C. and its hardness 0.4 mm.

Example 10.Zinc oxide, molten wax Example 11.Lead oxide parts hexane soluble Douglas fir wax was melted together with 3 parts lead oxide (litharge). The reactants were heated together at a temperature of C. with stirring for 20 minutes. The melted wax was then decanted from the residual lead oxide and permitted to harden. It melted at 85 C. and had a hardness of 0.9 mm.

Example 12.Cadmium oxide A quantity of hexane soluble Douglas fir wax was melted together with 2% by weight cadmium oxide. The mixture was maintained at a temperature of 150 C. for a time period of about 20 minutes. Upon cooling the beneficiated wax had a melting point of 83-85 C. and a hardness of 0.8 mm.

Example 13.Barium hydroxide A quantity of hexane soluble Douglas fir wax was melted together with 2% by weight barium hydroxide at a temperature of 110 C. This resulted in an increase in hardness to a value of 0.8 mm.

Example 14.Magnesium oxide, column operation Powdered magnesium oxide was mixed with celite in a ratio of 1:1 and placed in a column 50 cm. long and 10 mm. in diameter. A hot wax solution composed of 10 grams hexane soluble Douglas fir wax and 100 ml. hexane was passed through the column at a temperature of 60 C. During this operation the column and its contents were mamtamed at a temperature of 60 C. to avoid deposition of the wax.

The hexane solvent was removed from the eflluent mixture by distillation to yield the solid wax product. This had a melting point of 78-85" C. and a hardness of 0.6 mm. as compared with original values of 53 C. and 1.2 mm. respectively.

Example 15.Benzene soluble, hexane insoluble Douglas fir wax; magnesium oxide A quantity of that fraction of Douglas fir wax which 1s soluble in benzene but insoluble in hexane was melted with 2% by weight of magnesium oxide, the temperature being maintained at C. until the reaction was complete. The molten wax was decanted from any excess magnesium oxide and permitted to harden. The product Bvas a hard lustrous wax having a penetration value of only Example 16.Total wax; magnesium oxide 10 grams of the total wax content of Douglas fir bark obtalned therefrom by extraction of the bark with benzene was treated with 0.15 gram pulverized magnesium oxide. The reaction was carried out at 95 C. with stirr1ng unt1l the magnesium oxide had all dissolved. This requ red about one-half hour. The final product had a melting point of about 70 C. and a penetration of about 8.25 mm. as compared with original values of 56 C. and

Example 17.-Total wax; calcium hydroxide The procedure of Example 16 was followed with the exception that 0.15 part calcium hydroxide was substituted for the magnesium oxide of that example. In this case the final melting point was 69 C. and the final hardness 0.5 mm.

Example 18.Total wax; zinc oxide The procedure of Example 16 was followed with the exception that 0.15 part zinc oxide was employed in place of the magnesium oxide. In this case the final meltmg point was 100 C. and the penetration7 mm.

Example 19.-Lignil.= wax; calcium oxide Example 20.Carnauba wax This example illustrates the inapplicability of the presently described invent-ion to another vegetable wax, i. e. carnauba wax.

12 grams carnauba wax was boiled with'2'% calcium hydroxide (based on the weight of the wax) dissolved in 150 ml. of water. The wax-calcium hydroxide mixture was stirred vigorously for 15 to 30 minutes. It then was cooled. The water was decanted from the wax, and the latter broken up into a granular powder and air-dried. The final product had been degraded in properties, as evidenced by its weak structure, darkbrown color and lack of luster. Furthermore, its melting point after treatment was 79-30 (1., whereas its original melting point was 8082 Example 21.-Candelilla wax This example illustrates the inapplicability of the presently described process to candelilla wax, another vegetable wax.

The procedure of Example was followed, using however, candelilla wax instead of carnauba wax of that example. lts melting point remained unchanged at 6770 C.

Example 22.-B-eeswax This example illustrates the inapplicability of the present invention to an insect wax, beeswax.

The procedure of Example 20 was applied to Pioneer Brand Yellow Beeswax. After treatment the melting point of the wax was 58 C., the same as that of the untreated wax.

When grams beeswax was melted with 0.3 gram solid magnesium oxide for a time of minutes, its melting point remained unchanged at "SS-60 C. In addition, it contained the magnesium oxide in the form of white particles, indicating that no apparent reaction had taken place.

Having now described my invention in preferred embodiments, I. claim: I

l. The process which comprises reacting Douglas fir wax with at least about 0.1% by weight of at least one inorganic basic acting compound of a metal of the group consisting of lead and the Group H metals of the periodic chart, and recovering as a waxy product of improved properties the resulting combination of wax and basic acting compound.

2. The process which comprises reacting Douglas fir wax with at least about 0.1% by weight of at least one inorganic basic acting compound of an alkaline earth metal, and recovering as a waxy product of improved properties the resulting combination of wax and basic acting compound.

3. The process which comprises reacting Douglas fir wax with from about 0.1% to about 10.0% by weight of at least one inorganic basic acting compound of the group consisting of lead and the Group II metals of the periodic chart, and recovering as a wax product of improved properties the resulting reaction product of wax and basic acting compound.

4. The process which comprises reacting Douglas fir wax with from about 0.1% to about 10.0% by weight of at least one inorganic basic acting compound of zinc, and recovering as a wax product of improved properties the resulting combination of wax and basic acting zinc compound.

5. The process which comprises reacting Douglas fir wax with from about 0.1% to about 10.0% by weight of zinc oxide and recovering as a waxy product of improved properties the resulting combination of wax and zinc oxide.

6. The process which comprises reacting Douglas fir Wax with from about 0.1% to about 10.0% by weight of at least one inorganic basic acting compound of cal- 10 cium, and recovering as a waxy product of improved properties the resulting combination of wax and basic acting calcium compound.

7. The process which comprises reacting Douglas fir wax with from about 0.1% to about 10.0% by weight of at least one inorganic basic acting compound of magnesium, and recovering as a waxy product of improved properties the resulting combination of wax and basic acting magnesium compound.

8. The process which comprises reacting Douglas fir Wax with from about 0.1% to about 10.0% by weight of at least one inorganic basic acting compound of cadmium, and recovering as a waxy product of improved properties the resulting combination of wax and basic acting cadmium compound.

9. The process which comprises reacting Douglas fir wax with from about 0.1% to about 10.0% by weight of at least one inorganic basic acting compound of lead, and recovering as a waxy product of improved properties the resulting combination of wax and basic acting lead compound.

10. The process which comprises decolorizing crude Douglas fir wax by reacting it in the presence of moisture with an acid having a pH of less than about 5, the acid being employed in amount sufficient to reduce the pH of the wax to less than about pH 5, and reacting the wax with from about 0.1% to about 10.0% by weight of at least one inorganic basic acting compound of a metal of the group consisting of lead and the group II metals of the periodic chart, and recovering as a waxy product of improved properties the resulting combination of wax and basic acting compound.

11. The process of claim 10 wherein the acid isa mineral acid having a pH of less than about 5.

12. The process of claim 10 wherein the acid is sulfurous acid.

13. The process of claim 10 wherein the acid is an organic acid having a pH of less than about 5.

14. The process ofclaim 10 wherein the acid is oxalic acid.

15. The process which comprises melting Douglas fir wax, reacting the molten wax in the presence of moisture at a temperature of between about the melting point of the wax and the boiling point of water with an acid having a pH of less than about 5 used ina-mount sufficient to reduce the pH of the mixture to a value of less than about 5, thereby bleaching the wax, reacting the molten wax with from about 0.1% to about 10.0% by weight of at least one inorganic basic acting compound of a metal of the group consisting'of lead and the group II metals of the peridoic chart, and recovering as a waxy product of improved properties theresulting combination of wax and basic acting compound.

16. The process which comprises dissolving crude Douglas fir wax in a solvent therefor, reacting the resulting wax solution in the presence of moisture with an acid having a pH of less than about 5, the acid being used in amount sufficient to reduce the pH of the mixture to a value of less than about 5, thereby bleaching the wax, reacting the wax in said solvent with from about 0.1% to about 10.0% by weight of at least one inorganic basic acting compound of lead and the group II metals of the periodic chart, and recovering as a waxy product of improved color and increased melting point the resulting combination of wax and basic acting compound.

17. The process which comprises forming a suspension of Douglas fir wax in an aqueous medium, reacting the wax in the resulting aqueous suspension with an acid having a pH of less than about 5, the acid being employed in amount sufiicient to reduce the pH of the suspension to a value of less than about 5, reacting the resulting bleached wax in its aqueous suspension with from about 0.1% to about 10.0% by weight of at least one inorganic basic acting compound of a metal of the group cons1sting of lead and the group II metals of the periodic chart, and recovering as a waxy product of improved color and increased melting point and hardness the resulting combination of wax and basic acting compound.

18. The Douglas fir wax product having greater hardness than does the native wax, the wax product comprising the reaction product of Douglas fir wax and at least 0.1% by weight of at least one inorganlc basic acting compound of a metal of the group COHSlStlDg of lead and the group II metals of the period1c chart.

19. The Douglas fir wax product having greater hardness than does the native wax, the wax product comprising the reaction product of Douglas fir wax and from 0.1 to 10.0% by weight of at least one inorganic basic actlng compound of a metal of the group consisting of lead and the group II metals of the periodic chart.

20. The Douglas fir wax product having greater hardness and a higher melting point than does the native wax, the Wax product comprising the reaction product of Douglas fir wax and between 0.1% and 10.0% by weight of at least one inorganic basic acting compound of an alikaline earth metal.

21. The Douglas fir wax product having greater hardness and a higher melting point than does the native wax, the wax product comprising the reaction product of Douglas fir wax and between 0.1% and 10.0% by weight of at least one inorganic basic acting compound of calcium.

22. The Douglas fir wax product having greater hardness and a higher melting point than does the native wax. the wax product comprising the reaction product of Douglas fir wax and between 0.1% and 10.0% by weight of at least one inorganic basic acting compound of magnesium.

23. The Douglas fir wax product having greater hardness and a higher melting point than does the native wax, the wax product comprising the reaction product of Douglas fir wax and between 0.1% and 10.0% by weight of at least one inorganic basic acting compound of cadmium.

24. The Douglas fir wax product having greater hardness and a higher melting point than does the native wax, the wax product comprising the reaction product of Douglas fir wax and between 0.1% and 10.0% by weight of at least one inorganic basic acting compound of lead.

25. The wax product having a lighter color and greater hardness than does the native wax; the wax product comprising the reaction product of acid-bleached Douglas fir wax and at least 0.1% by weight of at least one inorganic basic acting compound of the group consisting of lead and the group II metals of the periodic chart.

26. The wax product having a lighter color and greater hardness than does the native wax, the wax product comprising the reaction product of acid-bleached Douglas fir wax and from 0.1% to 10.0% by weight of at least one inorganic basic acting compound of a metal of the group consisting of lead and the group II metals of the periodic chart.

27. The wax product having a lighter color and greater hardness than does the native wax, the wax product comprising the reaction product of acid-bleached Douglas fir wax and from 0.1% to 10.0% by weight of an inorganic basic acting compound of an alkaline earth metal.

28. The wax product having a lighter color and greater 12 hardness than does the native wax, the wax product comprising the reaction product of acid-bleached Douglas fir wax and from 0.1% to 10.0% by weight of an inorganic basic acting compound of calcium.

29. The wax product having a lighter color and greater hardness than does the native wax, the wax product comprising the reaction product of acid-bleached Douglas fir wax and from 0.1% to 10.0% by weight of an inorganic basic acting compound of zinc.

30. The wax product having a lighter color and greater hardness than does the native wax, the wax product comprising the reaction product of acid-bleached Douglas fir Wax and from 0.1% to 10.0% by weight of an inorganic basic acting compound of magnesium.

31. The wax product having a lighter color and greater hardness than does the native wax; the wax product comprising the reaction product of Douglas fir wax bleached with a mineral acid having a pH of less than 5, and from 0.1% to 10.0% by weight of at least one inorganic basic acting compound of a metal of the group consisting of lead and the group II metals of the periodic chart.

32. The wax product having a lighter color and greater hardness than does the native wax; the wax product comprising the reaction product of a sulfurous acid-bleached Douglas fir wax and from 0.1% to 10.0% by weight of at least one inorganic basic acting compound of a metal of the group consisting of lead and the group II metals of the periodic chart.

33. The wax product having a lighter color and greater hardness than does the native wax; the wax product comprising the reaction product of a sulfuric acid-bleached Douglas fir wax and from 0.1% to 10.0% by weight of at least one inorganic basic acting compound of a metal of the group consisting of lead and the group II metals of the periodic chart.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,108,282 Campbell et al. Feb. 15, 1938 2,383,629 Treacy Aug. 28, 1945 2,526,607 Kurth Oct. 17, 1950 FOREIGN PATENTS Number Country Date 2,100 Great Britain of 1885 9,264 Great Britain of 1842 OTHER REFERENCES Kurth et al.: Timberman, 49, l30-1 (1948), as abstracted in 42 C. A. 7977g (1948). 

21. THE DOUGLAS FIR WAX PRODUCT HAVING GREATER HARDNESS AND A HIGHER MELTING POINT THAN DOES THA NATIVE WAX, THE WAX PRODUCT COMPRISING THE REACTION PRODUCT OF DOUGLAS FIR WAX AND BETWEEN 0.1% AND 10.0% BY WEIGHT OF AT LEAST ONE INORGANIC BASIC ACTING COMPOUND OF CALCIUM. 